Theoretical Investigation of the Chemisorption of H2 and CO on the ZnO(101̄0) Surface

Inorganic Chemistry

Volumn 37, Issue 21, 1998, Pages 5482-5490

  Casarin, Maurizio ^a   Maccato, Chiara ^a   Vittadini, Andrea ^b  

^a UNIVERSITY OF PADOVA   (Italy)

^b CNR   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000395843     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic980443s     Document Type: Article

References (80)

1. Neumann, G. In Current Topics in Materials Science: Ed.; Kaldis, E., North-Holland: Amsterdam, 1981; Vol. 7, p 153.
2. (a) Kokes, R. J. Acc. Chem. Res. 1973, 6, 226 and references therein.
3. (b) Kokes, R. J.; Dent, A. L.; Chang, C. C.; Dixon, L. T. J. Am. Chem. Soc. 1972, 94, 4429.
4. Waddams, A. L. Chemicals from Petroleum, 3rd ed.; Wiley: New York, 1973.
5. Sojka, Z.; Herman, R. G.; Klier, K. J. Chem. Soc. Chem. Commun. 1991, 185.
6. (a) Henrich, V. E.; Cox, P. A. The Surface Science of Metal Oxides; Cambridge University Press: Cambridge, 1996.
7. (b) Henrich, V. E.; Cox, P. A. Appl. Surf. Sci. 1993, 72, 277 and references therein.
8. Barteau, M. A. J. Vac. Sci. Technol. A 1993, 11, 2162.
9. 2.
10. Hermann, R. G.; Klier, K.; Simmons, G. W.; Finn, B. P.; Bulko, J. B. J. Catal. 1979, 56, 407.
11. See, for example: Ghiotti, G.; Chiorino, A.; Bocuzzi, F. Surf. Sci. 1993, 287/288, 228.
12. Gay, R. R.; Nodine, M. H.; Henrich, V. E.; Zeiger, H. J.; Solomon, E. I. J. Am. Chem. Soc. 1980, 102, 6752.
13. Scarano, D.; Spoto, G.; Bordiga, S.; Zecchina, A.; Lamberti, C. Surf. Sci. 1992, 276, 281.
14. Anderson, A. B.; Nichols, J. A. J. Am. Chem. Soc. 1986, 108, 4742.
15. Nakatsuji, H.; Fukunishi, Y. Int. J. Quantum Chem. 1992, 42, 1101.
16. Nyberg, M.; Nygren, M. A.; Pettersson, L. G. M.; Gay, D. H.; Rohl, A. L. J. Phys. Chem. 1996, 100, 9054.
17. (a) Martins, J. B. L.; Andres, J.; Longo, E.; Taft, C. A. Int. J. Quantum Chem. 1996, 57, 861.
18. (b) Martins, J. B. L.; Taft, C. A.; Longo, E.; Andrés, J. J. Mol. Struct. (THEOCHEM) 1997, 398-399, 457.
19. Casarin, M.; Maccato, C.; Vittadini, A. Trends Inorg. Chem. 1996, 4, 43.
20. Casarin, M.; Maccato, C.; Vittadini, A. Surf. Sci. 1997, 377-379, 587.
21. 17
22. (a) Didziulis, S. V.; Butcher, K. D.; Cohen, S. L.; Solomon, E. I. J. Am. Chem. Soc. 1989, 111, 7110.
23. (b) Solomon, E. I.; Jones, P. M.; May, J. Chem. Rev. 1993, 93, 2623 and references therein.
24. (a) Casarin, M.; Tondello, E.; Vittadini, A. Surf. Sci. 1994, 303, 125 and references therein.
25. (b) Casarin, M.; Tondello, E.; Vittadini, A. Surf. Sci. 1994, 307-309, 1182.
26. Casarin, M.; Tondello, E.; Vittadini, A. Inorg. Chim. Acta 1995, 235, 151.
27. Casarin, M.; Favero, G.; Tondello, E.; Vittadini, A. Surf. Sci. 1994, 317, 422.
28. (a) Casarin, M.; Maccato, C.; Vittadini, A. Surf. Sci. 1997, 387. L1079.
29. (b) Casarin, M.; Maccato, C.; Vittadini, A. Chem. Phys. Lett. 1997, 280, 53.
30. Casarin, M.; Maccato, C.; Vittadini, A. Submitted for publication.
31. (a) Delley, B. J. Chem. Phys. 1990, 92, 508.
32. (b) Delley, B. J. Chem. Phys. 1991, 94, 7245.
33. 2 (type I) on ZnO(101̄0).
34. We consider chemically complete an atom with either a complete shell of nearest neighbors or one, belonging to the topmost layer, missing just one ligand.
35. Abrahams, S. C.; Bernstein, J. L. Acta Crystallogr. B 1969, 25, 1233.
36. (a) Duke, C. B. J. Vac. Sci. Technol. A 1992, 10, 2032.
37. (b) Duke, C. B.; Meyer, R. J.; Paton, A.; Mark, P. Phys. Rev. B 1978, 18, 4225 and references therein.
38. Mulliken, R. S. J. Chem. Phys. 1955, 23, 1833.
39. Jaffe, J. E.; Harrison, N. M.; Hess, A. C. Phys. Rev. B 1994, 49, 11153 and references therein.
40. Schröer, P.; Krüger, P.; Pollmann, J. In Proceeding of the 4th International Conference on the Formation of Semiconductor Interfaces; Langeler, B., Lurh, H., Mönch W., Pollmann, J., Eds.; World Scientific: Singapore, 1994.
41. (a) Wang, Y. R.; Duke, C. B. Surf. Sci. 1987, 192, 307,
42. (b) Wang, Y. R.; Duke, C. B. Phys. Rev. B 1987, 36, 2763.
43. Wang, Y. R.; Duke, C. B. Phys. Rev. B 1987, 37, 6417.
44. Wang, Y. R.; Duke, C. B.; Mailhoit, C. Surf. Sci. 1987, 188, L708.
45. Tight-binding calculations reported in ref 30 evaluate a 0.291 Å shift of the surface dimer center along the c axis towards the nearest second-layer zinc atom.
46. Rodriguez, J. A.; Campbell, C. T. J. Phys. Chem. 1987, 91, 6648.
47. 32 pointed out that their negatively charged cluster could be representative of a Cu doped ZnO based catalyst including alkali metals as promoters.
48. 20a-c
49. nn) are 0.39 (0.49) and 0.77 (0.89), respectively.
50. LaFemina, J. P. Surf. Sci. Rep. 1992, 16, 133.
51. Purcell, K. F.; Kotz, J. C. Inorganic Chemistry; Hot-Saunders International Editions: Japan, 1985.
52. Cotton, F. A.; Wilkinson, G. Advances in Inorganic Chemistry, 5th ed.; Wiley-Interscience: New York, 1988.
53. It is well-known that on low-index faces of oxides, CO is always adsorbed C-down oriented on surface cations; see, for example: Zecchina, A.; Scarano, D.; Bordiga, S.; Ricchiardi, G.; Spoto, G.; Geobaldo, F. Catal. Today 1996, 27, 403 and references therein.
54. Jaffe, J. E.; Hess, A. C. J. Chem. Phys. 1996, 104, 3348.
55. In general, the bonding scheme of M-CO carbonyl complexes (M is a transition metal atom in a low oxidation state) is characterized by a two-way electron flow, i.e., a σ donation from the CO 5σ HOMO into M empty levels and a π back-donation from the occupied M nd orbitals into the CO 2π lowest unoccupied molecular orbital (LUMO). The absence of any π back-donation from the Zn 3d AOs into the CO LUMO is due to a poor energy matching between the atom like Zn 3d AOs (see Figure 3) and the CO 2π virtual orbitals.
56. It has been shown that in the case of a chemical rather than a physical adsorption, the energies of the 1π and 5σ levels are, in contrast to in the gas phase, nearly (within a few tenths of an electronvolt) degenerate in the adsorbate. See: Freund, H. J.; Neumann, M. Angle-Resolved Photoemission. Theory and Current Application; Elsevier Science Publishers: Amsterdam, 1992.
57. -1.
58. Huber, K. P.; Herzberg, G. Molecular Spectra and Molecular Structures. Constants of Diatomic Molecules; Van Nostrand Reinhold Co.; New York, 1979: Vol. 4.
59. D'Amico, K. L.; McFeely, F. R.; Solomon, E. I. J. Am. Chem. Soc. 1983, 105, 6380.
60. Anderson, A. B.; Nichols, J. A. J. Am. Chem. Soc. 1986, 108, 1385.
61. Lin, J.; Jones, P.; Guckert, J.; Solomon, E. I. J. Am. Chem. Soc. 1991, 113, 8312.
62. Sayers, M. J.; McClellen, M. R.; Gay, R. R.; Solomon, E. I.; McFeely, F. R. Chem. Phys. Lett, 1980, 75, 575.
63. b OP (see Table 6).
64. 51 for CO chemisorbed on ZnO powder samples.
65. Bolis, V.; Fubini, B.; Giamello, E.; Relier, A. J. Chem. Soc., Faraday Trans. 1 1989, 95, 855.
66. a-C and C-O BLs are 2.201 and 1.121 Å, respectively.
67. 2+ ions of the polar ZnO(0001) surface.
68. Thibado, P. M.; Rohrer, G. S.; Bonnell, D. A. Surf. Sci. 1994, 318, 379.
69. Lin, J.; May, J. A.; Didziulis, S. V.; Solomon, E. I. J. Am. Chem. Soc. 1992, 114, 4718.
70. s symmetry. In the adopted framework, the symmetry plane corresponds to the xz one; thus, both x and z transform as a′, and the pure π character is accounted by the y coordinate (a″ in symmetry). This means that the a′ irreducible representation includes both "σ" (z) and "π" (x) contributions. Nevertheless, a careful inspection of the Mulliken population analysis indicates, for both clusters, a quite poor overlap between π and σ AOs of a′ symmetry, and consequently, a qualitative estimate of σ and π contributions to bonding interactions can be obtained by subtracting the a OP value from the a′ one and doubling the a′ OP value, respectively.
71. (a) Pasquali, M.; Floriani, C.; Gaetani-Manfredotti, A. Inorg. Chem. 1980, 19, 1191.
72. (b) Ruggiero, C. E.; Carrier, S. M.; Antholine, W. E.; Whittaker, J. W.; Cramer, C. J.; Tolman, W. B. J. Am. Chem. Soc. 1993, 115, 11285.
73. 2O(111) surface is coordinated to a single oxide ion.
74. Maccato, C. Tesi di Dottorato University of Padova, 1998.
75. Christe, K. O.; Charpin, P.; Soulie, E.; Bougon, R.; Fawcett, J.; Russel, D. R. Inorg. Chem. 1984, 23, 3756.
76. 2.
77. 2 is 18 kcal/mol.
78. -1 by analogy with hydrides.
79. Tsyganenko, A. A.; Lamotte, J.; Saussey, J.; Lavalley, J. C. J. Chem. Soc., Faraday Trans. 1 1989, 85, 2397.
80. -1 indicate that the relative modes can be described as a frustrated translation out of the symmetry plane (the former) and in the symmetry plane (the latter).